Covalent organic frameworks (COFs) have emerged as promising electrocatalysts due to their controllable architectures, highly exposed molecular active sites, and ordered structures. In this study, a series of porphyrin-based COFs (TAPP-x-COF) with various transition metals (Co, Ni, Fe) were synthesized via a facile post-metallization strategy under solvothermal synthesis. The resulting porphyrin-based COFs showed oxygen reduction reaction (ORR) activity with a trend in Co > Fe > Ni. Among them, TAPP-Co-COF exhibited the best ORR activity (E1/2 = 0.66 V and jL = 4.82 mA cm−2) in alkaline media, which is comparable to those of Pt/C under the same conditions. Furthermore, TAPP-Co-COF was employed as a cathode in a Zn-air battery, demonstrating a high power density of 103.73 mW cm–2 and robust cycling stability. This work presents a simple method for using COFs as a smart platform to fabricate efficient electrocatalysts.
4 February 2022 in Macromolecular Chemistry and Physics
A mild and efficient protocol for visible-light-photocatalyzed C5 nitration of 8-aminoquinoline derivatives was developed utilizing Cu(NO3)2∙3H2O as a nitro source. The reaction proceeded smoothly under very mild conditions, employing Acid Red 94 and a commercial household light bulb as an organic photosensitizer and a light source, respectively, making this synthetic procedure green and easy to operate. Furthermore, most products could be obtained through recrystallization, which enhanced the operational simplicity of this method.
Glycine (Gly), as one of the fundamental components of biomolecules, plays a crucial role in functional biomolecular coatings. The presence of structural defects and hydroxyl-containing functional groups in magnesium (Mg) materials, which are commonly used as biomedical materials, significantly affects their biocompatibility and corrosion resistance performance. This study computationally investigates the influence of vacancy defects and hydroxyl groups on the adsorption behavior of Gly on Mg(0001) surfaces. All potential adsorption configurations are considered through first-principles calculations. The findings indicate that stronger chemisorption occurs when Gly is positioned at the edge of the groove, where the surface has a vacancy defect concentration of 1/3. Among the four adsorption locations, the fcc-hollow site is determined to be the most favorable adsorption site for hydroxyl. The adsorption energy of Gly on the Mg(0001) surface containing the hydroxyl (−1.11 eV) is 0.05 eV more than that of on the Mg(0001) surface (−1.16 eV). The adsorption energies, electronic properties, charge transfer, and stable configurations are calculated to evaluate the interaction mechanism between Gly and defective surfaces. Calculated results provide a comprehensive understanding of the interaction mechanism of biomolecules on defective Mg surfaces and also indicate the directions for future experimental research.
Functional Arg-Gly-Asp (RGD) tripeptide has a tremendous potential in clinical applications to accelerate the endothelialization of Magnesium (Mg) alloy vascular stent surface. The interaction mechanism of RGD on different surfaces of Mg and Mg alloy is important for promoting the development of Mg alloy vascular stent, yet still unclear. In the present work, first-principles calculation within density functional theory (DFT) was performed to investigate the interaction mechanism. The electron redistribution, effect of alloying elements and changes in the density of states of the adsorption systems were studied. The results revealed that RGD interacted with different surfaces of Mg (0001), Mg(110) and Mg(101) through ligand covalent bond; the pronounced localization of electrons of Mg(110) and Mg(101) surfaces promoted the adsorption of RGD tripeptide compared with that on the Mg(0001) surface; Zn/Y/Nd alloying elements improved the adsorption of RGD. Calculated results could provide insight for the interaction mechanism of biomolecule on the Mg and Mg-based alloy surfaces, and point out some directions for the future experimental efforts.